Process for the reactivation of catalysts used in the dehydrogenation of organic compounds



Patented Apr. 23, 1940 UNITED STATES PATENT OFFICEJI I 2,198,195

. PROCESS FOR Tun REAo'nvA'rIoN or CATALYSTS USED IN THE neurone- GENATION or onoANIc COMPOUNDS Herbert P. A. Groll, Berkeley, and James Burgin, Oakland, Calif., assignors to Shell, Development Company, San Francisco, Calif., a corporation of Delaware 4 Claims. (01. 23-238) This invention relates to a process for the treatment of organic compounds whereby the treated compound is converted to an unsaturated compound containing fewer hyd rogen atoms but i the same number of carbon atoms to the molecule.

More particularly, the invention relates to a catalytic dehydrogenation process which comprises contacting a dehydrogenatable Organic compound, under substantially anhydrous conditions, with an activated alumina catalyst at an elevated temperature and for atime sufllcient to eflect dehydrogenation at apractical rate while avoidingconditions at which substantial cracking ofthe treated material or reaction products occurs.

' While providing a process broadly applicable with excellent results to the dehydrogenation of organic compounds, it is a particular object of 0 our invention to provide a practical and economical method for the technical-scale conversion of the saturatedhydrocarbons, such as are contained in or derived from petroleum and petroleum products, to the commercially valuable The oleiines of the aliphatic seriesare valuable raw materials for many purposes. 'They are readily convertible into valuable products ofindustrial importance as alcohols, ethers, esters, chlorn hydrins, glycols, acids, olefine oxides, etc. "In

addition, the higher olefines and the oleflne 1 polymerization and condensation products are useful as solvents and as fuels and as components which impart anti-knock and better burning 5 qualities to fuel mixtures.

The dehydrogenation of hydrocarbons is described in the literature. A variety of processes,

Due to the low yields of unsaturates obtained 3 and the diiiiculties of control so as to avoid excesscracking, the proposed processeshave failed to provide an economical, commercially feasible process. 0

It is known that at the higher temperatures s the parafilns undergo pyrolysis whereby small amounts of olefines are obtained. In addition to catalytic and non-catalytic, havebeen proposed. 3 obtama'ble and the dehydrogenation reaction proceeds so slowly that equilibrium conditions are practically unattainable and the yieldsof oleiines are commercially insignificant. a

0 Numerous catalysts have been proposed for accelerating the dehydrogenation reaction. The majority of these catalysts are too active and their efficient use requires the employment of low temperatures and high space velocities if disruption of the hydrocarbon molecule is to be avoided. For example,-nickel is a very active dehydrogenation catalyst but it is unsuitable due to the fact that its efficient use requires such low temperatures that equilibrium conditions are reached when only a small amount of the treated material hasbeen dehydrogenated, or such high space velocities that only a very small percentage is converted. Less active catalysts have been sug gested but the same marked disadvantages are also inherent in their use. They cannot be efiiciently employed in technical scale dehydrogenation processes at practical space velocities and at temperatures at which optimum conversions are attained while cracking is substantially avoided. Nowwe have found a catalyst the use of which brings the dehydrogenation of hydrocarbons within the field ofpractical utility. Our process comprises the use of an activated alumina catalyst under substantially anhydrous conditions. we may employ relatively low space velocities and maintain a high production of unsaturates pertime unit while employing temperatures at which optimum practical conversions are attained while substantially no cracking occurs.

The alumina employed can be prepared in a wide variety I of suitable manners from readily inexpensive materials. Said alumina may be activated by any 01 themethods known to the art. For example, the prepared alumina may be activated and rendered suitable for our purpose by calcining it at a temperature of from about 300 0 to about 800 c. If desired, aluminum hydrate prepared in any suitable manner may be converted to an activated alumina catalyst directly by heating it in this temperature range. The activation of the alumina is probably due to the change in, physical structure by reason of partial or complete dehydration occasioned by the calcination. The activation may beefiected under any suitable pressure.

in the Fickes-Sherwin modification ofthe Bayer process.

In addition to those herein described, other suitable modes of preparing and activating the alumina catalyst will be apparent to those skilled in the art. Conditions of preparation and activation of the catalyst should be such that the catalytic material is obtained in a porous form, since physical structure and surface phenomena may play a large part in its effectiveness.

Activated aliunina is a very economically employed catalyst due to its great stability under the conditions of its optimum activity. It retains its form with repeated use and reactivation over long periods. It is resistant to poisoning and retains its initial activity over long periods of continual use and, when there is a loss of activity due to poisoning, fatigue or tar and/or carbon deposition, the initial activity is readily and inexpensively restored.

The catalytic material in any suitable solid form as powder, granules, pellets, etc. or deposited on an inert carrier or in admixtin'e with an inert material is employed in manners customary in catalytic processes of this type. The desired quantity of the catalytic material, preferably in the form of granules, may be packed into a reaction chamber of any suitable material and heated to and maintained at the desired temperature while the. substantially dry material to be treated is passed into contact with it, preferably in the vapor phase at the desired space velocity and under the desired pressure of operation.

The term space velocity as used herein may be defined as the number of units of volume of gaseous material, measured at 0 C. and 76 cm. of Hg, contacted with a unit volume of catalyst per hour. I

The invention is preferably executed at temperatures of from about 500 C. to about 800 C. In some cases, higher or lower temperatures may beused. At lower temperatures the catalysts are less active and prohibitively low space velocities are required to attain practical conversions. At temperatures greater than about 800* C., prohibitively short contact times are required if cracking is to be avoided. As a consequence, the conversions are low due to the fact that equilibrium is not attained, The dehydrogenation of the lower paraffin hydrocarbons is preferably effected at temperatures below about 700 C. Al-

though the catalyst may be more active at higher temperatures, the rate of loss of activity is also greater and the process is generally more economically executed at lower temperatures at contact times favoring equilibrium conditions. The temperature to be employed is dependent upon the particular compound to be dehydrogenated, upon the space velocity, and upon the pressure of operation.

ulated that we may obtain practical conversions at a rate at which substantially no cracking occurs.

In the dehydrogenation of the parafiin hydro carbons, a greater production of the corresponding olefine per time unit and per quantity of catalyst is generally obtained when the space velocities near the upper limit of the suitable range are emoxygen and oxygen-containing mixtures.

ployed. This advantage is, however, usually of!- set by the lower oleiine content of the effluent gas and by the relatively much shorter period of activity of the catalyst. A

The invention is preferably executed in the sub stantial absence of water. Prior to their contact with the catalytic material, the materials to be treated, if they contain water in detrimental amounts, maybe dried in either the gaseous or liquid phase by any of the methods known to the art as, for example, by contact with drying agents as dehydrated calcium chloride, potassium carbonate, sodiumsulphate and the like. To avoid the formation of water during the course of the reaction, care is taken to exclude the presence of To exclude the presence of air, the reaction chamber containing the catalyst is preferably flushed out withan inert gas, as nitrogen, prior to its use.

Loss of activity of the catalyst, in the absence of specific catalyst poisons, is probably due to the deposition of carbon on the surface thereof in accordance with the reaction.

which occurs to a very limited extent simultaneously with the dehydrogenation reaction. Reactivation of ,the catalyst as herein described comprises removal of the deposited carbon by oxidizing it to carbon dioxide whereby the activity and space velocity at which the invention is exe- I outed. When the catalyst has lost its activity to the extent that its use is no longer practical, it can be easily and economically reactivated and its initial activity substantially restored without removing it from the catalyst chamber. The reactivation is effected by passing air or other suitable oxygen-containing gases into contact with the heated catalytic material. If desired the reactivation may be effected in the presence of an added inert gaseous material as steam, carbon dioxide, nitrogen, etc. For example, the catalyst may be reactivated by passing a mixture of steam and air over the heated catalyst. The reactivation may also be achieved by oxidation of the deposited carbon with carbon dioxide or steam alone. However, steam may harm the structure of the catalyst while with carbon dioxide the temperature required for the reactivation may become too high to be practical. The catalyst is'maintained at a temperature of from about 500 C, to about 800 C. while air is passed over it at a space velocity of from about to 500. After combustion has started the temperature of the catalyst can be controlled by regulating the flow of air. Temperatures above 800 C. are to be avoided since the activity of the catalyst may be permanently destroyed due probably to a change in physical structure. The time necessary to substantially restore the activity of the catalyst is dependent upon the amount of air or other oxidizing gas passed over it per time unit and upon the relative amount of carbon deposited thereon.

v When the process is executed under optimum "conditions of temperature and space velocity employing granules of activated alumina packed in a reaction tube having an average inside diameter of 2.0 cm. and a heating length of about 50 cm.. the reactivation is advantageously effected by passing air at the rate of about 500 c. c./min. (space velocity about 191) over the catalyst maintained at about 600 C. to 700 C. until no more hours of continuous operation. The average conversion for 30 hours of continuous operation was about 24.5%, while at the end of 89 hours oi. continuous operation the average conversion was still about 21.5%. The eflluent gas miigture con tained on the average about 20.6% isobutylene,

be detected in the eilluent gas mixture. During the regeneration, the temperature of the catalyst mass, due to the heat of combustion, reached about 675 C. The catalyst was substantially completely regenerated in about 11 hours.

Example III The catalyst employed was activated alumina in the form of granules (8-14 mesh).

The dehydrogenation was effected in a KA: steel tube having an average inside diameter of about 1.65 cm. and a heating length of about 50 cm. The reaction tube was packed with the catalyst and heated to a temperature of. about 600 C. while nitrogen was passed through it. When the temperature was at about 600 C., the nitrogen flow was stopped and substantially dry isobutane which had been previously preheated to about 450 to 500 C. was passed through the heated reaction tube at a spacevelocity of about 198 for a period of 48 hours. 'The average conversion of isobutane to isobutylene for this period was about 23%.

The catalyst .was regenerated by passing air through it at arate of about 500 c. c./min. while the temperature was maintained at from about 600 C. to about 700 C. The regeneration required about 8 hours.

The regenerated catalyst was utilized under substantially the same conditions as the fresh catalyst and was again. regenerated and reutilizd when there was a substantial'decrease in activity.

The following table shows the average butane to butylene conversions obtained over different time periods following repeatedregeneration of the catalyst.

Average percent conversion isobutane toisobutylene Catalyst A1301 8 I 12 i6 24 36 48 hrs. hrs. l hrs. hrs. hrs. hrs. hrs.

. 31.7 32.1 30.7 29.4 26.9 24.1 23.0 32.9 33.8 i 33.0 31.8 30.0 27.2 25.5 33.7 34.l I 33.7 32.6 31.5 29.4 27.9 25.1 29.6 i 30.3 30.4 29. 1' 27.4 25.0 18.0 25.0 27.6 28.6 28.5 27.4 12.3 l5.2 19.1 I 22.1 25.6 27.0 26.3 16.1 20.8 23.7 25.2 27.5 28.4 l2.0 l6.l 1 19.7 22.1 24.4 25.6 25.8 15.5 19.4 i 22.5 24.5 26.1 25.1 litl 22. 0 23.6 24.6 25.0

The average conversion over a 48 hour period was about andsince the catalyst was regenerated 9 times, the isobutylene produced per pound of catalyst employed was about 56.2 pounds.

Example IV An activated alumina catalyst was prepared by dissolving aluminum in an aqueous solution of NaOH and subsequently. passing CO2 into the solution to precipitate aluminum hydroxide. The

butane to butylene was attained after about 7 precipitatedaluminum hydroxide was separated. washed with water and dried at a temperature of about 600 C. About 35 c. c. of the dry activated alumina, in the form of granules, was packed in a quartz reaction tube having an inside diameter of about 1.04 cms. and a. heating length of about 65 cm.

The catalyst mass was maintained at an average temperature of about 575 C. while substantially dry normal butane was passed through it at an average space velocity of about 200 for a period of about 3.5 hours. The average conversion of n-butane to butylene was about 25%.

Example V A commercial activated alumina catalyst in the form of from about 8-14 mesh granules was packed in a steel reaction tube having an inside diameter of about 3 inches and a heating lengthof about 5 feet.

The packed reaction tube was inserted in a suitable furnace and heated. Nitrogen was passed through the reaction tube to displace, the air while the temperature of the catalyst mass was raised to about 600 0. While a temperature of about 600 C. was maintained, substantially dry isobutane, which had been previously preheated, was passed through the packed reaction tube at an average space velocity of about 300 for a period of about 16 hours.

During 16 hours of continuous operation, the average conversion of isobutane to isobutylene was about A maximum conversion of about was obtained after about 5.5 hours of op eration.

The ratio of isobutylene to total olefines in the efiluent gas mixture was about 0.75. The average composition of the eiiluent gas was:

Per cent Isobutylene 21.6 Lower olefines-- 7.0 Ethane-methane 7.0

Hydrogenm 31.8 Unreacted isobutane 32.6

At the end of the run, the catalyst was reactivated and its initial activity substantially restored by maintaining it at a temperature of from about 600 C. to about 700 C. while passing air through it until no more CO2 could be detected in the emuent gas.

Example VI A quartz reaction tube having an inside diamter of about 1 cm. and a heating length of about 50 cm. was packed with 8 to 14 mesh granules of an activated alumina catalyst and the packed tube inserted in a suitable electric furnac The 1 catalyst was maintained at a tempera are of about 600 C. while cyclohexane was'passed through it at a rate of about 1 c. c. of liquid per minute. About 50% of the cyclohexane passed through the reaction tube was dehydrogenated to benzene. The remainder was unchanged cyclohexane and a small quantity of decomposition products.

Example VII CO: can be detected in the efliuent gas. Under these conditions, to substantially restore the catalyst to its initial activity, one hour of reactivation is required for every eight hour period that the catalyst has been in use subsequent to the last reactivation. The catalyst may be repeatedly reactivated as above described, its initial qualities as a catalyst being restored at the end of each cycle.

Our process is broadly applicable to the dehydrogenation of hydrocarbons to compounds containing the same number of carbon atoms but fewer hydrogen atoms. Saturated hydrocarbons may be converted to the corresponding unsaturated compounds possessing one or a plurality of olefinic linkages or unsaturated hydrocarbons may be dehydrogenated to still more unsaturated compounds. For example, cyclo-hexane and cyclohexadiene may be converted to benzene, tetrahydronaphthalene to naphthalene, etc. The invention is applicable with excellent results to the conversion of paraflins containing two or more carbon atoms to the corresponding olefines. For example, the olefines of the same number of carbon atoms are prepared in excellent yields from ethane, propane, normal butane, isobutane, the pentanes, the hexanes, the heptanes and the like and their homologues and suitable substitution products. Such a straight or branched chain hydrocarbon may be linked to a cyclic radical as of the aromatic, alicyclic or heterocyclic series or the compound may comprise an alicyclic structure. For example, compounds as ethyl benzene, ethyl naphthalene and the like and their homologues, analogues and suitable substitution products are contemplated.

The compounds to be dehydrogenated may be treated severally or we may treat mixtures comprising more than one species. If desired, mixtures of one or more compounds to be treated with a relatively inert substance which will preferably exist in the gaseous state under operating conditions may be treated. For example, dehydrogenation may be effected in the presence oi materials as stable hydrocarbons, stable oleflnes. hydrogen, nitrogen, etc.v The material present may act as an inert diluent and, in addition, provide a suitable means of increasing the conversion of the material dehydrogenated by decreasing its partial pressure in the gaseous reaction mixture.

In many cases, the dehydrogenation may be advantageously efiected in'the initial presence of added hydrogen. The added hydrogen may exercise two favorable influences. It may act as a diluent and, in addition, due to the fact that hydrogen is an excellent heat-conducting gas, a more uniform temperature may be maintained in the reaction zone. Although the presence of a considerable quantity of hydrogen, in accordance with the law of mass action, represses the dehydrogenation, this unfavorable eil'ect is more than offset by the higher conversions due to the heat conductivity of the hydrogen.

Another mode of operating so as to decrease the partial pressure of the material to be dehydrogenated comprises effecting the reaction in the presence of} a suitable hydrogen acceptor. The dehydrogenation may be eifected in the presence of an unsaturated compound which when hydrogenated is less readily dehydrogenated than the material treated. As an example, sufilcient ethylene may be mixed with a compound to be dehydrogenated which possesses more than two carbon atoms so that the hydrogen liberated by the dehydrogenation hydrogenates the ethylene to ethane and thus removes free hydrogen irom the sphere of reaction. When operating in thismanner, the hydrogen acceptor is chosen with respect to the hydrogen donator and the conditions of its dehydrogenation so that the acceptor is more easily hydrogenated than the dehydrogenation product 01 the donator while the hydrogenated acceptor is less readily dehydrogenated than the donator.

Our invention may be executed at atmospheric, subatmospheric or moderately elevated pressures. Generally, the same is executed at atmospheric or moderately reduced pressures. Another suitable means of increasing the conversion by lowering the partial pressure of the material to be dehydrogenated, comprises eii'ecting reaction under a subatmospheric pressure. V

In accordance with the invention, we may treat hydrocarbon mixtures of saturates and unsaturates as occur in natural gas, cracked petroleum, petroleum products and mixtures resulting from the pyrogenetic treatment of shale oil, peat, asphalts, coals, etc. Technical oleflneparaflin-containing mixtures as the propane propylene cut, butane-butylene cut, pentaneamylene out, etc., may be treated and the ratio of higher oleilnes to paraflins increased or the cut or the original mixture from which it is derived may be treated by any suitable means as fractionation, condensation, absorption, extraction, etc., and the olefines removed therefrom prior to treatment of the saturates.

Motor fuels such as gasoline which contain small amounts of unsaturates can be improved, in accordance with our process, by passage over the heated activated alumina under the conditions herein specified. In this manner, the ratio of unsaturates to saturates in the fuel can be increased and its anti-knock quanlties enhanced.

The following examples are introduced for the purpose of illustrating modes of executing our invention and the results thereby obtained. It is to be understood that the invention is not to be limited to the specific materials or conditions of operation disclosed.

Example I side diameter of about 1.04 cms. and a heating length oi about 65 cms.

The catalyst mass was maintained at a temperature of about 650 C. while substantially dry propane was passed in contact with it at an average space velocity of about 514 (gas flow 300 c. c./min.) for a period of about 4 hours. The average conversion of propane to propylene was about 28.1%.

Example II Activated alumina in the form of granules (8-14 mesh) was packed in a KAz steel reaction tube having an average inside diameter of 1.6 cm. and a heating length of 50 cms.

Nitrogen was passed through the reaction tube while the temperature of the catalyst mass was raised to about 600 C. The temperature was maintained at about 600 C. while substantially dry isobutane, which had been previously preheated to a temperature of about 475 C., was passed through the catalyst mass at an average space velocity of 198.

The maximum conversion of about 34% iso- Our invention may be executed in a batch,intermittentorcontinuousmanner. Dehydrogenatable material that is not completely dehydrogenated on one passage through the reaction chamber may be reutilized in the same or another conversion stage. When executing the invention in an intermittent or continuous manner and recirculating the unreacted material, the conversion may be increased by intermittently or continuously withdrawing one or more of the conversion products from the system. For example, one or a plurality of conversion stages may be in com munication with one or more stages wherein the material subsequent to its issuance from the conversion stage or stages is treated for recovery of the unsaturates and/or hydrogen, and the unreacted material recirculated. For example, in the dehydrogenation of paraifins, the eiiiuent gases can be treated to remove their olefine content by passing them into contact with sulphuric acid,

sulphonic acid, phosphoric acid, sulphur dioxide,

etc. The gases thus denuded-of olefines may be recirculated over the catalyst. Alternatively, the exit gas may be brought into contact with a hydrogen-binding material as copper oxide. When the above means are resorted to, the gases can be treated until substantially all of the saturates are converted to unsaturates.

As a suitable means of operating continuously we may employ a plurality of dehydrogenating units, each in contact with a storage vessel containing the material to be treated, and utilize one or more reaction units while the catalytic material in one or more others is being regenerated as herein described without removing it from the reaction unit. When the catalyst in the converters in use loses its activity to the extent that the conversion per pass is no longer practicahthe material to be dehydrogenated is diverted to converters containing active catalyst. It is seen that in addition to providing a process for the technical scale production of valuable unsaturated compounds, the invention provides a novel process forthe production of hydrogen.

The terms dehydrogenation and dehydrogenating as used in this specification and the appended claims are intended to exclude those reactions in which oxygen or its equivalent combines with a hydrogen-containing compound to form a compound containing less hydrogen. Such reactions are entirely different from the type of reaction which occurs in accordance with our invention whereby hydrogen atoms are split from the treated compound resulting in a com pound containing less hydrogen and molecular hydrogen.

This is a division of our co-pending application, Serial No. 31,450, filed July 15, 1935.

We claim as our invention: 1. The process of reactivating an activated alumina catalyst the activity of which has been impaired by the deposition of carbon, tar and similar carbonaceous bodies on the surface thereof, which comprises subjecting the catalytic material to treatment with an oxygen-containing gas in the presence of steam at a temperature in the range of from 500 C. to 800 C. for a time not exceeding 11 hours whereby substantial restoration of the original activity ,of the catalyst is effected.

2. The process of reactivating an activated alumina which has been used as a catalyst to ef-- fect the catalytic dehydrogenation of a hydrocarbon containing at least two carbon atoms at a temperature of from 500 C. to 650 C. and has suffered loss of activity due to the deposition of carbon on the surface thereof, which comprises subjecting said catalytic material to treatment with a gas containing free oxygen at a temperature of from 500 C. to 800 C. for a time corresponding to about one hour for each eight hours of use subsequent to the last reactivation and not exceeding 8 hours whereby the deposited carbon is oxidized and substantially the initial activity of the catalyst restored. V

3. The process of reactivating an activated alumina which has been used as a catalyst to effect the catalytic dehydrogenation of a hydrocarbon containing at least two carbon atoms at a temperature of from ,500 C. to 650 C. and has suffered loss of activity due to the deposition of carbon on the surface thereof, which comprises subjecting said catalytic material to treatment with a gas containing freeoxygen at a temperature of from 500 C. to 650 C. for a time not exceeding 8 hours whereby the deposited carbon is oxidized and substantially the initial activity of the catalyst restored.

4. The process of reactivating an activated alumina catalyst, which has been prepared by the slow precipitation of an aluminum hydrate from its aqueous alkaline solution followed by calcination of the precipitated aluminum hydrate at a temperature of from 300 C. to 800 C., after said catalyst has suffered loss of activity during its use as a catalyst in a process for effecting the catalytic dehydrogenation of a dehydrogenatable hydrocarbon due to the deposition of carbon, tar and other carbonaceous bodies on the surface thereof, which comprises subjecting said catalytic material to treatment with air at a temperature of from 500' C. to 800 C. for a time not exceeding 8 hours whereby substantially the initial activity of the catalyst is restored.

HERBERT P. A. GROLL. JAMES BURGIN. 

